Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound

ABSTRACT

A catalyst for polymerizing olefins is the product resulting from heating in an inert hydrocarbon diluent a mixture of (A) an organomagnesium material, (B) an organic hydroxyl-containing material, (C) a reducing halide source and (D) a transition metal compound.

BACKGROUND OF THE INVENTION

This invention relates to a new catalyst composition useful forinitiating and promoting polymerization of one or more α-olefins and toa polymerization process employing such a catalyst composition.

It is well known that olefins such as ethylene, propylene, and 1-butenein the presence of metallic catalysts, particularly the reactionproducts of organometallic compounds and transition metal compounds canbe polymerized to form substantially linear polymers of relatively highmolecular weight. Typically such polymerizations are carried out atrelatively low temperatures and pressures.

Among the methods for producing such linear olefin polymers, some of themost widely utilized are those described by Professor Karl Ziegler inU.S. Pat. Nos. 3,113,115 and 3,257,332. In these methods, the catalystemployed is obtained by admixing a compound of a transition metal ofGroups 4b, 5b, 6b and 8 of Mendeleev's Periodic Table of Elements withan organometallic compound. Generally the halides, oxyhalides andalkoxides or esters of titanium, vanadium and zirconium are the mostwidely used transition metal compounds. Common examples of theorganometallic compounds include the hydrides, alkyls and haloalkyls ofaluminum, alkylaluminum halides, Grignard reagents, alkali metalaluminum hydrides, alkali metal borohydrides, alkali metal hydrides,alkaline earth metal hydrides and the like. Usually, the polymerizationis carried out in a reaction medium comprising an inert organic liquid,e.g., an aliphatic hydrocarbon and the aforementioned catalyst. One ormore olefins may be brought into contact with the reaction medium in anysuitable manner, and a molecular weight regulator, such as hydrogen, isoften added to the reaction vessel in order to control the molecularweight of the polymers. Such polymerized processes are either carriedout at slurry polymerization temperatures (i.e., wherein the resultingpolymer is not dissolved in the hydrocarbon reaction medium) or atsolution polymerization temperatures (i.e., wherein the temperature ishigh enough to solubilize the polymer in the reaction medium).

Following polymerization, it is common to remove catalyst residues fromthe polymer by repeatedly treating the polymer with alcohol or otherdeactivating agent such as an aqueous basic solution. Such catalystdeactivation and/or removal procedures are expensive both in time andmaterial consumed as well as the equipment required to carry out suchtreatment.

Gessell's U.S. Pat. Nos. 4,244,838 and 4,246,383 and pendingapplications Ser. No. 192,959 filed Oct. 1, 1980 and 192,960 filed Oct.1, 1980 and now abandoned by Gessell, Gibbs and Fuentes, Jr., disclosecatalysts prepared by employing an organic hydroxyl-containing material.However, such catalysts are directed only to the resultant solidreaction product which must be separated from the liquid portion andwashed. It would be desirable to employ a catalyst which does notrequire the recovery of the solid reaction product and the attendantwashing steps.

The present invention provides a catalyst for polymerizing α-olefinswhich catalysts are sufficiently efficient so as to not require theirremoval from the polymer and their preparation does not require recoveryand washing of the solid reaction product.

SUMMARY OF THE INVENTION

The present invention is directed to a catalytic product resulting from

(I) admixing in an inert hydrocarbon diluent and in an atmosphere whichexcludes moisture and oxygen

(A) at least one hydrocarbon soluble organomagnesium material;

(B) at least one organic hydroxyl-containing material;

(C) at least one reducing halide source; and

(D) at least one transition metal (Tm) compound; and

(II) heating the resultant mixture at a temperature of from about 35° C.up to the boiling point of the inert hydrocarbon diluent, preferablyfrom about 40° C. to about 100° C., for a time to permit substantialreaction of the resultant mixture as indicated by a change in color ofthe mixture; and wherein

(1) the components are added in the order (A), (B), (C) and (D) or (A),(B), (D) and (C); and

(2) the components are employed in quantities so as to provide thefollowing atomic ratios

Mg:Tm of from about 0.1:1 to about 50:1, preferably from about 0.5:1 toabout 20:1 and most preferably from about 1:1 to about 5:1;

Cl:Mg of from about 2:1 to about 5:1, and preferably from about 3.5:1 toabout 4.5:1; and

the OH:total number of hydrocarbyl groups attached to a metal atom incomponent (A) is from about 0.5:1 to about 1.2:1 and preferably fromabout 0.8:1 to about 1.05:1.

A further aspect of the invention is a process for polymerizingα-olefins or mixtures thereof which comprises conducting thepolymerization in the presence of the aforementioned catalysts.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The organomagnesium materials which are suitably employed in the presentinvention include those represented by the formula R₂ Mg.xMeR'_(x')wherein each R is independently a hydrocarbyl group and each R' isindependently a hydrogen, hydrocarbyl or hydrocarbyloxy group, Me is Al,Zn or B, x has a value from 0 to 10 and x' has a value equal to thevalence of Me.

The term hydrocarbyl as employed herein refers to a monovalenthydrocarbon group such as alkyl, cycloalkyl, aryl, aralkyl, alkenyl andsimilar hydrocarbon groups having from 1 to about 20 carbon atoms withalkyl having from 1 to 10 carbon atoms being preferred.

The term hydrocarbyloxy as employed herein refers to monovalentoxyhydrocarbon group such as alkoxy, cycloalkoxy, aryloxy, aralkoxy,alkenoxy and similar oxyhydrocarbon groups having from 1 to about 20carbon atoms with alkoxy groups having from 1 to 10 carbon atoms beingthe preferred hydrocarbyloxy groups.

The quantity of MeR'_(x'), i.e. the value of x, is preferably theminimum amount which is sufficient to render the magnesium compoundsoluble in the inert solvent or diluent which is usually a hydrocarbonor mixture of hydrocarbons. The value of x therefore is from zero toabout 10, usually from about 0.2 to about 2.

Particularly suitable organomagnesium compounds include, for example,di-(n-butyl) magnesium, n-butyl-sec-butyl magnesium, diisopropylmagnesium, di-n-hexyl magnesium, isopropyl-n-butyl magnesium,ethyl-n-hexyl magnesium, ethyl-n-butyl magnesium, di-(n-octyl)magnesium, butyl octyl magnesium, butylethylmagnesium.1/2triisobutylaluminum, di-n-hexyl magnesium.1/2 triisobutylaluminum andsuch complexes as di-n-butyl magnesium.1/3 aluminum triethyl,di-(n-butyl) magnesium.1/6 aluminum triethyl, mixtures thereof and thelike.

Suitable hydroxyl-containing organic compounds include, for example,alcohols, glycols, polyoxyalkylene glycols, mixtures thereof and thelike.

Suitable such compounds include those represented by the formulas

    R(O-R').sub.n OH and Z((O-R').sub.n O-R").sub.n',

wherein each R is a hydrocarbyl group having from 1 to about 20,preferably from 1 to about 10, carbon atoms or a halogen; each R' isindependently a divalent hydrocarbyl group having from 1 to about 20,preferably from 1 to about 10, carbon atoms; each R" is independentlyhydrogen or a hydrocarbyl group having from 1 to about 20, preferablyfrom 1 to about 10, carbon atoms, at least one of which is hydrogen; Zis a multivalent organic group containing from 2 to about 20 carbonatoms; n has a value from zero to about 10; and n' has a value of from 2to about 10.

Particularly suitable organic hydroxylcontaining compounds includealcohols such as for example methyl alcohol, ethyl alcohol, n-propylalcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol,tert-butyl alcohol, octadecyl alcohol, glycols, 1,2-butylene glycol,1,3-propylene glycol, 1,4-butanediol, 1,6-hexane diol, other hydroxylcontaining compounds such as, for example, glycerine, trimethylolpropane, hexane triol, phenol, 2,6-di-tert-butyl-4-methylphenol,mixtures thereof and the like. Also suitable are the adducts of ethyleneoxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide,styrene oxide or mixtures of such oxides with the previously mentionedor other hydroxyl-containing compounds such as pentaerythritol, sucrose,sorbitol and the like, as well as the alkyl and aryl cappedhydroxyl-containing compounds so long as there remains at least 1hydroxyl group per molecule.

Suitable reducing halide sources include those represented by theformulas

    Al(R.sup.3).sub.3-m X.sub.m and B(R.sup.3).sub.3-m X.sub.m

including mixtures thereof wherein each R³ is independently hydrogen ora hydrocarbyl group as hereinbefore defined, and m has a value from 1 to2.

Particularly suitable reducing halides include, for example,ethylaluminum dichloride, diethylaluminum chloride, ethylaluminumsesquichloride, ethylboron dichloride, diethylboron chloride, mixturesthereof and the like.

Suitable transition metal compounds which can be employed include thoserepresented by the formula TMY_(n) X_(z-n), wherein Tm is a transitionmetal in its highest stable valence state and being selected from groupsIV-B, V-B and VI-B of the Periodic Table of the Elements; Y is oxygen,OR" or NR₂ "; R" is hydrogen or a hydrocarbyl group having from 1 toabout 20 carbon atoms; X is a halogen, preferably chlorine or bromine; zhas a value corresponding to the valence of the transition metal, Tm; nhas a value of from zero to 5 with the value of z-n being from zero upto a value equal to the valence state of the transition metal, Tm.

Particularly suitable transition metal compounds include, for example,titanium tetrachloride, titanium tetrabromide, dibutoxy titaniumdichloride, monoethoxy titanium trichloride, isopropoxytitaniumtrichloride, tetraisopropoxytitanium, tetra-n-propoxytitanium,tetra-n-butoxytitanium, chromyl chloride, vanadium oxytrichloride,zirconium tetrachloride, tetrabutoxyzirconium, vanadium tetrachloride,mixtures thereof and the like.

Suitable organic inert diluents in which the catalyst can be preparedand in which the α-olefin polymerization can be conducted include, forexample, liquefied ethane, propane, isobutane, n-butane, isopentane,n-pentane, n-hexane, the various isomeric hexanes, isooctane, paraffinicmixtures of alkanes having from 8 to 12 carbon atoms, cyclohexane,methylcyclopentane, dimethylcyclohexane, dodecane, eicosane industrialsolvents composed of saturated or aromatic hydrocarbons such askerosene, naphthas, etc., especially when freed of any olefin compoundsand other impurities, and especially those having boiling points in therange from about -50° to about 200° C. Also included as suitable inertdiluents are benzene, toluene, ethylbenzene, cumene, decalin and thelike.

Suitable cocatalysts or activators with which the catalysts of thepresent invention can be reacted, contacted or employed in thepolymerization of α-olefins includes those aluminum, boron, zinc ormagnesium compounds represented by the formulas Al(R³)_(3-a) X'_(a),B(R³)_(3-a) X'_(a), MgR³ ₂, MgR³ X', ZnR³ ₂ or mixtures thereof whereinR³ is as previously defined; X' is a halogen, preferably chlorine orbromine; and a has a value of from zero to 2, preferably zero to 1 andmost preferably zero.

Particularly suitable cocatalysts or activators include, for example,diethylaluminum chloride, ethylaluminum dichloride, diethylaluminumbromide, triethylaluminum, triisobutylaluminum, diethylzinc,dibutylmagnesium, butylethylmagnesium, butylmagnesium chloride,diisobutylaluminum hydride, isoprenylaluminum, triethylboron,trimethylaluminum, mixtures thereof and the like.

The cocatalysts or activators are employed in quantities such that theatomic ratio of the Al, B, Mg, Zn or mixtures thereof to Tm is fromabout 0.1:1 to about 1000:1, preferably from about 5:1 to about 500:1and most preferably from about 10:1 to about 200:1.

The catalyst and cocatalyst or activator may be added separately to thepolymerization reactor or they may be mixed together prior to additionto the polymerization reactor.

Olefins which are suitably homopolymerized or copolymerized in thepractice of this invention are generally any one or more of thealiphatic α-olefins such as, for example, ethylene, propylene, butene-1,pentene-1, 3-methylbutene-1, 4-methylpentene-1, hexene-1, octene-1,dodecene-1, octadecene-1, 1,7-octadiene and the like. It is understoodthat α-olefins may be copolymerized with one or more other α-olefinsand/or with small amounts i.e., up to about 25 weight percent based onthe polymer of other polymerizable ethylenically unsaturated monomerssuch as styrene, α-methylstyrene and similar ethylenically unsaturatedmonomers which do not destroy conventional Ziegler catalysts. Mostbenefits are realized in the polymerization of aliphatic α-monoolefins,particularly ethylene and mixtures of ethylene and up to 50 weightpercent, especially from about 0.1 to about 40 weight percent ofpropylene, butene-1, hexene-1, octene-1, 4-methylpentene-1,1,7-octadiene or similar α-olefin or α-diolefin based on total monomer.

In the polymerization process employing the aforementioned catalyticreaction product, polymerization is effected by adding a catalyticamount of the catalyst composition to a polymerization zone containingα-olefin monomer, or vice versa. The polymerization zone is maintainedat temperatures in the range from about 0° to about 300° C., preferablyat slurry polymerization temperatures, e.g., from about 0° to about 95°C., more preferably from about 50° to about 90° C., for a residence timeof from about 15 minutes to about 24 hours, preferably from about 30minutes to about 8 hours. It is generally desirable to carry out thepolymerization in the absence of moisture and oxygen and a catalyticamount of the catalytic reaction product is generally within the rangefrom about 0.0001 to about 0.1 milligram-atoms transition metal perliter of diluent. It is understood, however, that the most advantageouscatalyst concentration will depend upon polymerization conditions suchas temperature, pressure, diluent and presence of catalyst poisons andthat the foregoing range is given to obtain maximum catalyst yields.Generally in the polymerization process, a carrier which may be an inertorganic diluent or excess monomer is generally employed. In order torealize the full benefit of the high efficiency catalyst of the presentinvention care must be taken to avoid oversaturation of the diluent withpolymer. If such saturation occurs before the catalyst becomes depleted,the full efficiency of the catalyst is not realized. For best results,it is preferred that the amount of polymer in the carrier not exceedabout 50 weight percent based on the total weight of the reactionmixture.

It is understood that inert diluents employed in the polymerizationrecipe are suitable as defined hereinbefore.

The polymerization pressures preferably employed are relatively low,e.g., from about 10 to about 500 psig. However, polymerization withinthe scope of the present invention can occur at pressures fromatmospheric up to pressures determined by the capabilities of thepolymerization equipment. During polymerization it is desirable toagitate the polymerization recipe to obtain better temperature controland to maintain uniform polymerization mixtures throughout thepolymerization zone.

Hydrogen is often employed in the practice of this invention to controlthe molecular weight of the resultant polymer. For the purpose of thisinvention, it is beneficial to employ hydrogen in concentrations rangingfrom about 0 to about 80 volume percent in the gas or liquid phase inthe polymerization vessel. The larger amounts of hydrogen within thisrange are found to produce generally lower molecular weight polymers. Itis understood that hydrogen can be added with a monomer stream to thepolymerization vessel or separately added to the vessel before, duringor after addition of the monomer to the polymerization vessel, butduring or before the addition of the catalyst. Using the general methoddescribed, the polymerization reactor may be operated liquid full orwith a gas phase and at solution or slurry polymerization conditions.

The monomer or mixture of monomers is contacted with the catalyticreaction product in any conventional manner, preferably by bringing thecatalyst composition and monomer together with intimate agitationprovided by suitable stirring or other means. Agitation can be continuedduring polymerization. In the case of more rapid reactions with moreactive catalysts, means can be provided for refluxing monomer andsolvent, if any of the latter is present and thus remove the heat ofreaction. In any event, adequate means should be provided fordissipating the exothermic heat of polymerization, e.g., by coolingreactor walls, etc. If desired, the monomer can be brought in the vaporphase into contact with the catalytic reaction product, in the presenceor absence of liquid material. The polymerization can be effected in abatch manner, or in a continuous manner, such as, for example, bypassing the reaction mixture through an elongated reaction tube which iscontacted externally with suitable cooling medium to maintain thedesired reaction temperature, or by passing the reaction mixture throughan equilibrium overflow reactor or a series of the same.

The polymer is readily recovered from the polymerization mixture bydriving off unreacted monomer and solvent if any is employed. No furtherremoval of impurities is required. Thus, a significant advantage of thepresent invention is the elimination of the catalyst residue removalsteps. In some instances, however, it may be desirable to add a smallamount of a catalyst deactivating reagent. The resultant polymer isfound to contain insignificant amounts of catalyst residue.

The following examples are given to illustrate the invention, and shouldnot be construed as limiting its scope. All parts and percentages are byweight unless otherwise indicated.

In the following examples, the melt index values I₂ and I₁₀ weredetermined by ASTM D 1238 conditions E and N respectively. The apparentbulk density was determined as an unsettled bulk density according tothe procedure of ASTM 1895 employing a paint volumeter from theSargent-Welch Scientific Company (catalog no. S-64985) as the cylinderinstead of the one specified by the ASTM procedure.

GENERAL PROCEDURE

In each of the following examples, unless otherwise stated, the catalystcomponents were blended while in a gloved box filled with dryoxygen-free nitrogen.

In the examples, the dibutylmagnesium was a commercial material obtainedas a solution in a heptane-hexane mixture from the Lithium Corporationof America, the dihexylmagnesium was a commercial material obtained as ahexane solution from the Ethyl Corporation, and the butylethylmagnesiumwas a commercial material obtained as a heptane solution from TexasAlkyls, Inc. All ratios are molar ratios unless otherwise indicated. The1.46 molar diethylaluminum chloride, 0.616 molar triisobutylaluminum and0.921 molar triethylaluminum were obtained as solutions in hexane fromEthyl Corporation or Texas Alkyls, Inc.

PREPARATION OF STOCK SOLUTION A

In a dry box filled with dry, oxygen-free nitrogen, a stock solution ofa hydrocarbon soluble magnesium complex was prepared by consecutivelymixing while stirring 628 ml of 0.637 molar butylethylmagnesium (400mmoles) 325 ml of 0.616 molar triisobutylaluminum (200.2 mmoles) and thedropwise addition of 105.3 ml of neat n-propyl alcohol (1408.9 mmoles).An exotherm was observed upon addition of the n-propyl alcohol and thetemperature was maintained at about 40° C. for controlling additionrate. The resultant mixture was allowed to cool to room temperature.Since some of the hexane was lost through evaporation, the volume wasthen adjusted to 800 ml by the addition of hexane. The resultant stocksolution was water white with no visible particulates and was 0.5 molarwith respect to magnesium.

PREPARATION OF STOCK SOLUTION B

A stock solution of a hydrocarbon soluble magnesium complex was preparedby mixing 148.8 ml of 0.84 molar di-n-hexylmagnesium (125 mmoles), 101.5ml of 0.616 molar triisobutylaluminum (62.5 mmoles) and 32.8 ml of neatn-propylalcohol (437.5 mmoles). An exotherm was observed during then-propyl alcohol addition and the temperature was maintained at about40° C. by controlling the rate of addition. The solution was dilutedwith n-hexane such that the resultant volume was 500 ml and was 0.25molar with respect to magnesium.

EXAMPLE 1

A. Preparation of Catalyst

To a stirred 500 ml beaker containing 75 ml of magnesium stock solutionA (37.5 mmoles Mg) and 100 ml of n-hexane were added 3.72 ml of 3.34molar tetraisopropoxytitanium (12.5 mmoles). No color change wasobserved and the mixture remained a solution. Then 49 ml of 1.53 molarethylaluminiumdichloride (75 mmoles) in n-hexane were added dropwise. Avery pale yellow slurry resulted upon completion of theethylaluminumdichloride addition. The slurry was heated to 65°-70° C.for one hour (3600 s) resulting in a tan colored slurry with a brownsupernatant liquid.

B. Polymerization

To a stirred 1.8 liter autoclave was added 1 liter of dry, oxygen-freen-hexane. While maintaining a small nitrogen purge, 1.1 ml of 0.921molar triethylaluminum were added followed by an aliquot of the catalystprepared in A above containing 0.005 mmoles of titanium. The reactor wassealed, purged with hydrogen and heated to 85° C. Hydrogen was thenadded so that the reactor pressure was 50 psig (345 kPa) at 85° C.Ethylene was introduced into the reactor and was employed to maintain atotal reactor pressure of 170 psig (1172 kPa). After 2 hours (7200 s),the reactor was cooled to room temperature and vented. The reactor sealwas broken and the contents were filtered, air-dried and then driedunder vacuum overnight at about 70° C. The yield of dry polyethylenepowder was 127 g. The properties and efficiency were:

melt index (I₂): 2/21

bulk density, lbs/ft³ (kg/m³): 17.2 (276)

catalyst efficiency, g PE/g Ti: 843,000

COMPARATIVE EXPERIMENT A

A. Catalyst Preparation

To a stirred 500 ml beaker containing 75 ml of magnesium stock solutionA (37.5 mmoles Mg) and 100 ml of n-hexane were added 3.72 ml of 3.36molar tetraisopropoxytitanium (12.5 mmoles). No color change wasobserved and the mixture remained a solution. Then 49 ml of 1.53 molarethylaluminumdichloride (75 mmoles) were added dropwise resulting in apale yellow slurry. No heat was applied during preparation of thiscatalyst.

B. Polymerization

1. In a manner similar to Example (1-B), ethylene was polymerized withthe catalyst prepared in (A) above employing the following components.3.26 ml of 0.921 molar (3 mmoles) triethylaluminum and an aliquot ofcatalyst from (A) aged at room temperature for 1.7 hours (6120 s)containing 0.015 mmole Ti were employed. The polymerization resulted in66 g of dried polymer having a melt index of 0.21 and a bulk density of9.9 lbs/ft³ (159 kg/m³). The catalyst efficiency was 92,000 g polymer/gTi.

2. Another polymerization was made employing the procedure of Example(1-A) using 2.17 ml of 0.921 (2 mmoles) of triethylaluminum and analiquot of the catalyst prepared in (A) above which had been aged for 24hours (86.4 ks) at room temperature and contained 0.01 mmole oftitanium. The polymerization activity was complete after 1.25 hours(4500 s) as indicated by zero ethylene flow into the reactor. Thepolymerization produced 25 g of dried polymer having a melt index (I₂)of 0.15 and a bulk density of 11.6 lbts/ft³ (186 kg/m³). The catalystefficiency was 32,000 g polymer/g Ti.

EXAMPLE 2

A. Catalyst Preparation

To a 100 ml aliquot of magnesium stock solution B containing 25 mmolesdi-n-hexylmagnesium, 12.5 mmoles tri-isobutylaluminum and 87.5 mmolesn-propyl alcohol was added 0.37 ml of 3.36 M tetraisopropoxytitanium(1.24 mmoles). The solution remained water white. Then 32.6 ml of 1.53molar ethylaluminumdichloride (49.9 mmoles) were added dropwise. Theresultant white slurry was heated for 30 minutes (1800 seconds) at 65°C. resulting in a purplish tan colored slurry. The Mg/Ti ratio of thiscatalyst was 20/1.

B. Polymerization

Employing the procedure of Example (1-B) ethylene was polymerized using1.1 ml of 0.616 molar trisobutylaluminum (0.68 mmoles) and an aliquot ofthe catalyst prepared in (A) above containing 0.0035 mmoles Ti. A twohour (7200 s) polymerization produced 91 g of dried polymer having amelt index (I₂) of 0.37 and a bulk density of 11.1 lbs/ft³ (178 kg/m³).The efficiency was 541,000 g polymer/g Ti.

EXAMPLE 3

A. Catalyst Preparation

To a stirred 500 ml beaker were added 100 ml of 0.637 molarbutylethylmagnesium (63.7 mmoles), 53 ml of 0.616 molartriisobutylaluminum (32.6 mmoles), 17.3 ml of neat n-propyl alcohol(230.8 mmoles) and 1.9 ml of neat tetraisopropoxytitanium (6.38 mmoles).Then 90 ml of 1.53 molar ethylaluminumdichloride (137.7 mmoles) wereadded at 65° C. over a period of about two hours (7200 s). The resultantcatalyst slurry was reddish in color and the Mg/Ti ratio was 10/1.

B. Polymerization

Employing the procedure of example (1-B), a two hour (7200 s)polymerization was conducted using 1.3 ml of 0.616 triisobutylaluminum(0.8 mmoles) and an aliquot of catalyst containing 0.004 mmole Tiprepared in (A) above. The polymerization produced 142 g of driedpolymer having a melt index (I₂) of 1.8 and a bulk density of 20.5lbs/ft³ (327 kg/m³). The catalyst efficiency was 730,000 g polymer/g Ti.

C. Polymerization

Employing the procedure of Example (1-B), a two hour (7200 s)polymerization was conducted using 0.9 ml of 0.921 molartriethylaluminum (0.83 mmoles) and an aliquot of the catalyst preparedin (A) above containing 0.04 mmoles of Ti. The polymerization produced282 g of dried polymer having a melt index (I₂) of 1.5 and a bulkdensity of 22.5 lbs/ft³ (360 kg/m³). The catalyst efficiency was1,190,000 g polymer/g Ti.

EXAMPLES 4 TO 9

A. Catalyst Preparation

Several catalysts were prepared by adding sequentially to a 500 mlbeaker in a dry, oxygen-free atmosphere the following:

(1) 75 ml of stock solution A containing 37.5 mmolesbutylethylmagnesium, 18.75 mmoles of triisobutylaluminum and 132 mmolesof n-propyl alcohol;

(2) a titanium compound;

(3) 49 ml of 1.53 molar ethylaluminumdichloride (75 mmoles).

The mixture was then heated to about 70° C. for 1-11/2 hours (5400 s).The catalyst preparation variables are given in Table I.

B. Polymerization

The various catalysts prepared in (A) above were employed in thepolymerization of ethylene employing the procedure of Example (1-B). Thevariables and results are given in Table II.

                  TABLE I                                                         ______________________________________                                        EXAMPLE                    mmoles                                             NUMBER        Ti COMPOUND  Ti                                                 ______________________________________                                        4             Ti(OiPr).sub.4 *                                                                           18.75                                              5             Ti(OiPr).sub.4                                                                             37.5                                               6             Ti(OiPr).sub.4                                                                             75                                                 7             TiCl.sub.4   12.4                                               8             TiCl.sub.4   37.5                                               9             TiCl.sub.4   75                                                 ______________________________________                                         *tetraisopropoxytitanium                                                 

                                      TABLE II                                    __________________________________________________________________________              EXAMPLE NO.                                                                   4    5    6    7    8    9                                          __________________________________________________________________________    H.sub.2 Pressure,                                                                       50 (345)                                                                           50 (345)                                                                           50 (345)                                                                           50 (345)                                                                           50 (345)                                                                           50 (345)                                   psig (kPa)                                                                    Ti, mmoles                                                                              0.020                                                                              0.010                                                                              0.050                                                                              0.005                                                                              0.005                                                                              0.010                                      ATE*, mmoles                                                                            1.000                                                                              20.000                                                                             2.500                                                                              1.000                                                                              1.000                                                                              0.500                                      Polymer produced,                                                                       121  155  43   191  73   110                                        grams                                                                         Melt Index, I.sub.2                                                                     1.9  1.5  6.4  7.6  2.7  1.9                                        Bulk Density,                                                                           15.6 (250)                                                                         11 (176)                                                                           9.5 (152)                                                                          22.4 (359)                                                                         18.3 (293)                                                                         13.4 (215)                                 lbs/ft.sup.3 (kg/m.sup.3)                                                     Efficiency,                                                                             126,000                                                                            32,000                                                                             18,000                                                                             797,000                                                                            305,000                                                                            230,000                                    g polymer/g Ti                                                                __________________________________________________________________________

The Mg/Ti, Cl/Mg, and OH/total number of hydrocarbyl groups (TNHG)attached to the metal atom ratios for each of the examples andcomparative experiment are given in the following Table III.

                  TABLE III                                                       ______________________________________                                        EXAMPLE OR                                                                    COMPARATIVE                                                                   EXPERIMENT NO.                                                                              Mg/Ti     Cl/Mg   OH/TNHG                                       ______________________________________                                        1             3.0       4.0     1.0                                           A             3.0       4.0     1.0                                           2             20.0      4.0     1.0                                           3             10.0      4.3     1.0                                           4             2.0       4.0     1.0                                           5             1.0       4.0     1.0                                           6             0.5       4.0     1.0                                           7             3.0       4.0     1.0                                           8             1.0       4.0     1.0                                           9             0.5       4.0     1.0                                           ______________________________________                                    

I claim:
 1. A catalytic product resulting from(I) admixing in an inert hydrocarbon diluent and in an atmosphere which excludes moisture and oxygen(A) at least one hydrocarbon soluble organomagnesium material; (B) at least one organic alcoholic hydroxyl-containing material; (C) at least one reducing halide source; and (D) at least one transition metal (Tm) compound; and (II) heating the resultant mixture at a temperature of from about 35° C. up to the boiling point of the inert hydrocarbon diluent, for a time to permit substantial reaction of the resultant mixture as indicated by a change in color of the mixture; and wherein(1) the components are added in the order (A), (B), (C) and (D) or (A), (B), (D) and (C); and (2) the components are employed in quantities so as to provide the following atomic ratiosMg:Tm of from about 0.1:1 to about 50:1; Cl:Mg of from about 2:1 to about 5:1; and the OH:total number of hydrocarbyl groups attached to a metal atom in component (A) is from about 0.5:1 to about 1.2:1.
 2. A catalytic product of claim 1 wherein(1) Component (A) is represented by the formula R₂ Mg.xMeR'_(x') wherein each R is independently a hydrocarbyl group having from 1 to about 20 carbon atoms; each R' is independently a hydrogen, hydrocarbyl or hydrocarbyloxy group having from 1 to about 20 carbon atoms; Me is Al, Zn or B; x has a value from zero to 10 and is sufficient to render the organomagnesium component hydrocarbon soluble; and x' has a value equal to the valence of Me; (2) Component (B) is represented by the formulas R--O--R')_(n) OH and Z----O--R')_(n) O--R")_(n') wherein each R is a hydrocarbyl group having from 1 to about 20 carbon atoms or a halogen; each R' is independently a divalent hydrocarbyl group having from 1 to about 20 carbon atoms; each R" is independently hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms, at least one of which is hydrogen; Z is a multivalent organic group containing from 2 to about 20 carbon atoms; n has a value from zero to about 10; and n' has a value of from 2 to about 10; (3) component (C) is represented by the formulas Al(R³)_(3-m) X_(m) and B(R³)_(3-m) X_(m) including mixtures thereof wherein each R³ is independently hydrogen or a hydrocarbyl group as above defined, X is a halogen and m has a value from 1 to 2; (4) component (D) is represented by the formula TMY_(n) X_(z-n), wherein Tm is a transition metal in its highest stable valence state and being selected from groups IV-B, V-B and VI-B of the Periodic Table of the Elements; Y is oxygen, OR" or NR"₂ ; R" is hydrogen or a hydrocarbyl group having from 1 to about 20 carbon atoms; X is a halogen, preferably chlorine or bromine; z has a value corresponding to the valence of the transition metal, Tm; n has a value of from zero to 5 with the value of z-n being from zero up to a value equal to the valence state of the transition metal, Tm; (5) the atomic ration of Mg:Tm is from about 0.5:1 to about 20:1; (6) the atomic ratio of Cl:Mg is from about 3.5:1 to about 4.5:1; and (7) the ratio of OH groups in component (B): total number of hydrocarbyl groups attached to a metal atom in component (A) is from about 0.8:1 to about 1.05:1.
 3. A catalytic product of claim 2 wherein(1) in component (A) each R and R' is a hydrocarbyl group having from 1 to about 10 carbons, Me is Al and x has a value of from about 0.2 to about 2; (2) component (B) is an alcohol having from 1 to about 10 carbon atoms; (3) component (C) is an aluminum alkyl halide wherein each R³ is independently a hydrocarbyl group having from 1 to about 10 carbons and X is chlorine; (4) in component (D), Tm is titanium; and (5) the atomic ratio of Mg:Tm is from about 1:1 to about 5:1.
 4. A catalytic product of claim 3 wherein(1) component (A) is a complex of butylethylmagnesium and triisobutylaluminum or a complex of di-n-hexylmagnesium and triisobutylaluminum; (2) component (B) is n-propyl alcohol; (3) component (C) is ethylaluminumdichloride; and (4) component (D) is tetraisopropoxytitanium or titanium tetrachloride. 